Alkylated polyphenyl ether sulfonates



United States Patent ce 3247245 Patented Apr. 19, 196.6

3,247,245 R{:O X M-%Q=\,I t rm ALKYLATED PQLYRH g YL ETHER J? h J:

SU FQ h Arthur 5. Teot and Edward P. Merica, Midland, Mich,, 5 E l I" l assignors to The Dow Chemical Company, Midland, l. J, Mich a prp rat m o Delawa e 6 471 (Em B) No The symbol 5 represents a phenylene moiety, the symbols y and 2 represent integers from 0 to 5 and the sum The present invention relates to a novel class of organic 10 of lib? Integers y and Z 1 t0 4, X represents a middle intermediates and their sulfonated derivatives. More halogen, d the ym and M h ve t e Same Si particularly the present invention concerns alkylated poly- 33 1 t f b QE E ation A nd B are fi ethers i polysulfclmlc acid a 2 3 2232? earrie d'oii i irii l i e rnz nr i er of the will knovf/n Uli mann con nove com un s c i :3; g tg ii i i f ll i gzo ul 15 densation reaction, that is, in the presence of a catalytic amount of copper at temp ratures of from about 220 7 v to 270 C. or inthe manner taught in the copending r 1 application Serial No. 142,486, wherein the employment R O O of a copper salt of an alkylated diphenyl oxide, sulfonic L l acid is taught, or in the presence of a copper salt of a n (1) compound corresponding to generic Formula II above (303mm (5031mm :geprgn M in the formula has been substituted with i I The following examples illustrate the method of prepa- R O 0 (8031mm ration of the compounds which fall under the generic V L i (II) Formula I above, but are not to be construed as limiting:

' Example 1 wherein R i'epfisents an alklfld adical havinagikaat1i 132E316 100Cg .7(92.g5 grliozlezolzisf)pgrrfiggpslgiinolhvgjiolgaizmgisg:

toms, re resen s ro en or an i E 23 an i f o l 4, wpresents an pellets) was added thereto and the mixture was stirred inte er from 0 to 2 and the sum of the ms equal at and heated up to 160170 C. at reduced pressure (ca.

leas t 3, and until the sums of the, ms equal n+3 no more 20 to remove the w t of reaction. The than 1 sulfonate moiety is attachedto each phenylene 1 511312?gglutlondzgasaelologeilguntiglitmbgizgncga frgleze moiety. The novel compou ds w thin the generic Fori h6g1 oxidppwer added I g. ixture W pgrrggi g mula I are useful intermediates in the preparation 0 11,, y e e Ihis m as I an at 5-2 as t: m anest ti l-tethered aserati:

e t tureuissaeunerm a aiiife s mosi hef 5131s about 700 F. Thus, these madistilled 3 f P- Y P G Y -P-Phenoxyphenyl terials find utility as transformer fluids, lubricants and 40 ethgrzwas O g edT fh -yi gab ing pointoff214-20 c.

the like. at mm. -g. V is represents a yield 0 82.7 o. In-

The novel compounds of generic Formula II have been frared p s py co m d h s t r tested and found to be useful as intermediates in pre- E l 2 paring soluble copper catalysts and a e e surfactants 532 g. (2.86 moles) of phenoxyphenol 92% meta in Stmng a1ka1i m eta1 hydfoxlde Solutlons' The isomer) was mixed with 145 g. (2.2 moles) of potassium P E Y 15. 1 .5.1 .1 P P P W c0mposltlons hydroxide (85% pellets) and the mixture was stirred of caustic solutions useful In cleaning articles of manuand heated to 1600 at reduced pressure (ca 20 mm.

facture- Further utlhty f comPounds 9? Wlthm Hg) to remove the water of reaction. The resulting the generlc Formula; H 15 the1r ability to Solublh? Such solution was cooled to 100 C. and 10 g. of copper dust materials as defoaming agents in the strong caustic soluand 373 g. of dodecylcmomdiphenyl oXidQ were added nons- This mixture was stirred and heated at ZOO-220 C. 'for GENERAL METHOD OF PREPARATION ()F 4 hours. It was then cooled to 100, diluted with toluene ALKYLATED PQLY-PHENYL S' and filtered. The filtrate was distilled and 150 g. of para 1 I (para-dodecylphenoxy)phenyl meta-phenoxyphenyl ether The new alkylatse-d polyghenyl ethers Gf Formuha was obtained having a boiling point of 256278 C. at 0.2

be by (A) reiactmg an alkyl phenol (p em 18 mm. Hg. The yield was 28.7%. Infrared spectroscopy usede hCI'ClIl and hereinafter to refer to a hydroxy aroconfirmed the Structure.

matic compound of the benzene series, hydroxy phenyl Exam [8 3 ethersand hydro y polyphenyl ethers) or its alkali metal I H t EP 1 1 1 salt with a halophenyl ether in the presence of a catalytic t n af rzlggner stimb ar 01i iample idemp a IIHX:

amount of a pper catalyst or an alkylated halobenure od 1 0 me adromo p eny fox e a; d 1para1 zene can be reacted with an alkali metal galttl of hydroxy brocrlno tilphenyl oxire a1; dpaaloe i1o idplatrafi- CII'OE'IYO aepeyd 01 he 1 ther. It is to be understoo t at ese com- 0X1 6, ere wa pop 0 '1 e gou ri tls :Zn be prepared in the presence of copper as a spectroscopy as 60% para-nonylphenyl meta-phenoxycatal st accordin to the followin general equations: phenyl th r and 40% para-nonylphenyl para-phenoxyy g a phenyl ether having a boiling point at 0.8 mm. Hg of V 208 212 C. in a yield of 77.1%. E l X 4 H Example 4 y In amanner similar to Example 1, employing a mix- R- -O, -O.-O H ture of 60% meta-bromodiphenyl oxide and 40% para- L L bromodiphenyl oxide in place of para-ibromodiphenyl oxide and para-dodecylphenol in place of nonylphenol,

Example 5 Example 6 Example 7 TABLE II.SURFACE ACTIVE PROPERTI PHENYL ETHER The alkylated polyphenyl ethers prepared in the above phenyl ether (60% meta) in 400 milliliters of methylene chloride. The reaction mixture was maintained at 27 C. throughout the addition. Stirring was continued for an additional 45 minutes. Immediately upon cessation of stirring the reaction mixture was poured into 500 milliliters of water and neutralized with 50% sodium hydroxide. The mixture separated into two layers, an organic layer and an aqueous layer. The aqueous layer was separated and dried on a drum dryer. As a result of these operations ca. 50 grams of sodium para-nonylphenyl meta-phenoxyphenyl ether trisulfonate was obtained. Analysis showed the material to have an average of 3.7 sulfonate groups per molecule.

The following table shows the results obtained employing various ethers of Examples 2 through 6 and various amounts of sulfur trioxide as reactants in the man ner of the foregoing Example 7.

The table also sets forth the solubility of the respective compounds in various concentrations of aqueous caustic. The solubility was determined by mixing 1% by weight of the respective compounds in 99% by weight of one of the various aqueous caustic solutions.

TABLE L-SODIUM ALKYLPOLYPHENYL ETHER SULFONATES Avg. no. Solubility in NaOH Alkylate Moles S0; sulionate used groups on molecule 30% 50% -N0ny1phenyl m-phenoxyphenyl 4. 1 3. 7 S S s p ether (60% meta) 4. 4 4. U S S s p-Nonylphenyl p-phenoxyphenyl 4. 1 3.2 S S I etheri i 2 p-D0deoy1phenyl m-phenoxpyhenyl 1 3 S S I e e (60% meta) 4 0 S s s 4. 1 3. 4 S S I p-Dodecylphenyl p-phcnoxyphenyl 4. 4 3 5 s S I ether 5. 5 4.1; g s -D odecylphenoXY Dhenyl m- 3. 1 3. p ghenoxy phenyl eth)er907,1rnet121i)i 4. l 4. 1 S S I -(pDodecylphenoxy p eny p-p e p oxyphcnyl other 4. 4 4. 3 s S I The For purposes of comparison with the solubility of the novel compounds the solubilities of various ionic surfactants is set forth in the table below:

Example 8 The following table records the surface active properties of the compounds of the present invention.

ES OF 0.1% SOLUTIONS OF THE LISTED ALKYLATED POLY- SULFONATES IN DISTILLED WATER Average 110. Surface Interfacial Wetting Alkylate sulfonate tension tension Foam height Foam height time groups on (dyneslcnl) (dynes/cm.) (imtlal) (mm.) (5 min.) (m1n.) (m1n.)

molecule 6 79 48 1.18 p-Nonylphenyl m-phenoxyphenyl ether.-. 1 25 0 8 24. 8 20 0.7 p-Nonylphenyl p-phenoxyphenyl ether 20' 2 5O 8 0 9 3. 1 34. 7 9. 0 145 g D c 'l hen lmlienoxy hen -l ester- 3.3 33. 9 9. 6 p ode y p y p p y i 4.0 40.5 12.9 50 15 0.8 3. 4 40. 9 14. 4 188 3 -Do ec l hen l henoxy hen lether 3.5 42. 3 19. 9 1 p d y p y p p p y i 4.8 43.3 16.0 142 14g p- -D odecylphenoxy)phenyl m- 3. 1 35. 8 9. 5 5

ghenoxyphenyl ethejnflnulnui 4. 1 42. 9 15. 2 115 0. 47 -Dodec l henox en prep ii iixylphe y i etheri inf): 4. 3 40. 9 17. 7 105 10 0. 55

Example 9 The following table sets forth the properties of the compounds in aqueous 5% NaOH solutions.

TABLE III.SURFACE ACTIVE PROPERTIES IN 5% NaOH OF THE LISTED ALKYLATED POLYPHENYL ETHER SULFONATES Average No. Surface Interfaeial Alkylate snlionate tension tension Foam height Foam height groups on (dynes/cm.) (dynes/cm.) (initial) (mm.) (5 min.) (111111.) molecule 0.1% Solutions:

p-Dodecylphenyl p-phenoxyphenyl ether 4. 8 46. 9 13. 7 153 10 p-Nonylphunyl m-phenoxyphenyl ether. 3. 7 35. 8 6. 5 135 0.3% Solutions:

p-Dodecylphenyl m-phenoxy'phenyl other 3. 45. 5 11. 9 175 35 pNonylphenyl m-phenoxyphenyl ether 3. 7 37. 2 7. 4 175 0 We claim:

Example 10 To further illustrate the unique properties of the sulfonated alkylated polyphenyl ethers of the present invention a bottle Washing concentrate composition was prepared to illustrate the ability of the compounds not only to go into solution in strong caustic but to solubilize other materials in the strong caustic.

To 94 parts by weight of an aqueous 50% caustic (NaOH) solution was added 6 parts of an aqueous solution of sodium glucoheptanate.

To the same solution was added with mild stirring 1% by weight of an aqueous 50% sodium p-dodecylphenyl p-phenoxyphenyl ether pentasulfonate solution. The entire solution became clear almost immediately and did not settle out upon standing for several days.

The solution prepared above can be diluted to 5% caustic concentration and employed as a bottle washing composition for content and label removal from bottles.

The sulfonated compounds of the present invention can be employed to prepare bottle washing concentrates having the following general compositions:

Percent by Weight Alkylated sulfonated polyphenyl ethers 0.05-5 sequestering agents, such as sodium gluconate or sodium glucoheptanate .6-10

Antifoam agent 0-.6

Aqueous -50% alkali metal hydroxide Balance It is to be further understood that various other ingredients normally employed in such compositions can be solubilized in the concentrate. One such material is a foam control agent of the generic class of nonionic surfactants such as the ethylene oxide-butylene oxide condensates with organic compounds having at least three active hydrogens such as the alkylenepolyamine, alkanolamines, glycols, glycerines and the like. One such suitable compound is that obtained by condensing 15 moles of ethylene oxide then 4.5 moles of butylene oxide with 1. An alkylated polyphenyl ether sulfonic acid having the formula I 3M) m '1 .fit,

wherein R represents an alkyl radical having from 6 to tetrasulfonate.

4. Sodium paradodecylphenyl para-phenoxyphenyl ether tetrasulfonate.

5. Sodium paradodecylphenyl meta-phenoxyphenyl ether tetrasulfonate.

6. Para-(para-dodecylphenoxy)phenyl metaphenoxyphenyl ether tetrasulfonic acid.

7. Para- (para-dodecylphenoxy)phenyl para-phenoxyphenyl ether tetrasulfonic acid.

References Cited by the Examiner UNITED STATES PATENTS 2,081,876 5/1937 Prahl 260-512 X 2,140,824 12/1938 Vernon 260613 2,500,107 3/ 1950 Weichselbaum 252--161 2,517,636 8/1950 David 252161 2,555,371 6/1951 Prutton 260-512 2,739,171 3/1956 Linn 260-613 2,854,477 9/ 1958 Steinhauer 2605 12 2,940,929 6/ 1960 Diamond 260-613 X 3,006,852 10/1961 Barnum et al a- 260613 X LORRAINE A. WEINBERGER, Primary Examiner.

LEON ZITVER, Examiner. 

1. AN ALKYLATED POLYPHENYL ETHER SULFONIC ACID HAVING THE FORMULA 